JPS5943063A - Monoazo dye, manufacture and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is suitable for dyeing natural and synthetic polyamides with an aqueous dyebath, has a hue ranging from yellow to red, and has improved The purpose of this invention was to provide a new monoazo dye that has excellent dye fastness, particularly light fastness.

According to the present invention, it has been discovered that monoazo dyes having the following general formula (]) satisfy the above requirements.

Therefore, the present invention relates to a monoaiso dye represented by the following general formula ().

In the formula, K is an amino or alkoxybenzene residue, an amino or alkoxynaphthalene residue, a naphthol residue, an aminonaphthol residue, a pyrazolone residue, an aminovirazole residue, means a residue of indole, a residue of naphthoimitasole, a residue of diphenylamine, a residue of tetrahydroquinoline, or a residue of acetoacetamide, these groups can be further substituted, R is hydrogen , halogen, 01 6-alkyno, trifluoromethyl, carboxyl, or =, s. o2-C
．． t-a-alkyl, -S O21- Rl, group (wherein, R1 is a substituted or unsubstituted Fe,=Rou or naphthyl-ct-n-alkyl group, R2 and R3, etc. are mutually independent) hydrogen, or substituted or unsubstituted Cl-6
-alkyl group, still Cs-t-cycloalkyl group,
and R4 means a substituted or unsubstituted fluorocarbon group), and "?X means hydrogen, CI-4-alkyl, C,=4-alkoxy, or halogen. , where the base N=N−K
is attached to the phenyl ring at the ○1 position relative to the -SO2 group, and K is the residue of aminonaphthalene sulfonamide or 2-amino-8. -Hydroxynaphthalene-6-sulfonic acid, R in formula '(1) cannot be hydrogen or chlorine.

．． Coupling component? Residue K can contain the usual substituents in azo dyes.

For example, it can contain substituents such as:
・ ... Methyl, ethyl, provil, isoprovil, butyl,
Alkyl groups having 1 to 4 carbon atoms such as isobutyl, butyl, tert-butyl; methoxy, ethoxy to propyloxy:, isopropyloxy, butoxy, isobutoxy, . Alkoxy groups having 1 to 4 carbon atoms such as sec-butoxy, tert-butoxy, phenoxy, alkanoylamino groups having 1 to 6 carbon atoms such as acetylamino or propionylamino, penzoylamino, amino groups. Toepa N
H2, methylamino, ethylamino, dimethylamino,
diethylamino, cyanoethylamioctahydroxyethylamino, dihydroxyethylamino, cyclohexylamino, pendylamino and phenylamino, carboxylic acid ester groups such as methoxyluponyl and ethoxyluponyl, trifluoromethyl, nitro, cyano,
Acetyl, methylsulfonyl, carbamoyl, sulfamoyl, ureido, hydroxyl, carboxyl, sulfo, sulfomethyl and halogens such as fluorine, chlorine, bromine and fiber-reactive groups.

When R and X mean halogen, they are each independently a fluorine atom and a chlorine atom is a bromine atom.

Examples of the C+-a-alkyl group represented by R include a methyl group, an ethyl group, a probyl group, an isopropyl group, a butyl group, an isobutyl group, a butyl group, a tert-butyl group,
The pentyl group is the hexyl group. Preferably R is a methyl group.

Examples of the -802 C+-a-alkyl group represented by R are methyl-, ethyl-, proby-, isopropyl-, butyl-, imbutyl-, crown-butyl, tert-
Butyl, pentyl or hexylsulfonyl groups come into consideration. Preferably R means a methylsulfonyl group or an ethylsulfonyl group.

When R means phenyl or naphthyl-01-4=alkyl group, examples of the group are benzyl group, phenethyl group or naphthylmethyl group. in this case,
The aryl moiety is, for example, CI-4- such as methyl.
Further substituted by an alkyl group, a C1-4-alkoxy group such as methoxy, ethoxy, a halogen such as fluorine, chlorine, bromine, an alkanoylamino group having 1 to 6 carbon atoms in the case of acetylamino, hydroxyl or carboxyl. can be done.

Examples of the C1-6-alkyl group represented by R2 and R3 include, independently of each other, a methyl group, an ethyl group, a probyl group, an isopropyl group, a butyl group, a butyl group, a tert
-Butyl, pentyl or hexyl groups come into consideration. In this case, the alkyl groups can be further substituted, for example by halogens such as fluorine, chlorine, bromine, hydroxyl, cyano and alkoxy such as methoxy, ethoxy, propoxy, isopropoxy, butoxy. Examples include β-hydroxyethyl, β-methoxyethyl, β-cyanoethyl, β-chloroethyl, and the like.

The cycloalkyl group represented by R2 and R3 is
Cyclopentyl, cyclohexyl, cycloheptyl, etc. are considered independently of each other, and these include, for example, halogens such as fluorine, chlorine, bromine, CI-4-alkyl such as methyl, ethyl, proyl, isoprobyl,
It can be further substituted by auto-4-alkogoxy such as methoxy. An example is the methylcyclohexyl group.

When R4 means a phenyl group, it is a C
I-4 -C such as alkyl group, methoxy, ethoxy
It may be further substituted by a 1-4-alkoxy group, a halogen such as fluorine, chlorine, or bromine.

When X in formula (1) means a C1-4-alkyl group, it means, for example, a methyl group, an ethyl group, a proyl group,
It can be isoprobyl, butyl, especially monobutyl, isobutyl or tert-butyl.

If X means c,-4-alkoxy, it can be, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy or tert-butoxy. .

Preferred monoaiso dyes of formula (1) are those of formula (IIK) in which a) X is bonded to the sulfophenyl ring at the p-position relative to one -SO2 group, and b) R is bonded to one -SO2 group. and C) the group N=N-K is bonded to the phenyl ring at the 0- or p-position relative to the -so2 group, and
It is bonded to the phenyl ring at one position.

The monoazo dye of formula (1) has its coupling component (K)
can be substituted with fiber-reactive groups. Examples of suitable fiber-reactive groups are aliphatic ones such as acryloyl, mono, di- or tri-chloro or mono-, di- or tri-bromoacryloyl or -methacryloyl, such as 1Co-CI{=C:
H-α,. :-CO-Cα=C}{2,=CO-CH=
CHBr, -CO. CBr==CH2, -CO-
C B r-CT[l r%+CO=Cα2CI{-
CHa, and also -CO=Cα2CFI-Cool{,
'-CO=CH=Cα-COOH, 2-chloropionyl, . 3-phenylsulfonylpionyl, 3-
Methylsulfonyl, vinylsulfonyl, β
-Chloroethylsulfonyl, β-sulfatoethynolesnorrefonino, β-methylsulfonylethylsulfonyl, ? β-Phenylsulfonylethylsulfonyl, 2-fluoro2-chloro-3,3-difluorobutane-1-carbonyl, 2,2,3.3=tetrafluorobutane-1-carbonylbutane=1- sulfonyl,
β-(2,2,3,3-tetrafluorocyclobuto-1
-yl) monoacryloyl, α- or β-alkyl- or aryru-sulfonyl-acryloyl, e.g.
α-1 is β-methylsulfonylacryloyl.

Particularly suitable reactive groups for synthetic polyamides and wools are: chloroacetyl, promoacetyl, α,β-dichloro-or α,β-dibromopionyl, α-chloro-1 or α-promo. Acryloyl, 2,4-difluoro-5-chloropyrimid-6-yl, 2,4,. 6-trifluoropyrimid-5-yl, 2,4-dichloro-5
-methyl-sulfonylpyrimid-6-yl, 2,4-difluoro-5-methyl-sulfonylpyrimid-6-yl, 2,4-difluorotriazin-6-yl, and a fluorotriazinyl group of the formula It is the corresponding global triazinyl group. In the above formula, R6 means a substituted or unsubstituted amino group, an unetherified or etherified oxy group, or a thio group, such as NHt group, C1-C. - an amino group mono- or di-substituted by an alkyl group, C1 -C4
-Alkoxy group, self-1011 alkylmerkabuto group, ・
Arylamino, especially phenylamino, or phenylamino substituted by methyl, methoxy, chlorine or especially sulfo, phenoxy, monosulfophenoxy, disulfophenyloxy and the like. - Examples of starting materials for the introduction of such triazine groups include: 2. 4'-difluoro or 2,4-dichloro-6-aminotriazine, 2,'4-difluoro or 2,'4-dichloro-6-methylaminotriazine, 2
,4-difluoro or 2,4-dichloro-6-ethylaminotriazine, 2,4-difluoro or'
2,4-Jik. Rollo 6-Hue. Nylaminotriazine, 2,4-difluoro or 2,4-dichloro-6-
(2',3/-still 4'-sulfophenyl)mono-aminotriazine, 2,4-difluorostill 2,4-dichloro-6-(2',11'-still 3/,4/
One stroke or two. /． 5/1 or 4'j 5'-disulfofene-diyl) monoaminotriazine, 2,4-difluoro or 2,4-dichloro-6-dimethylaminotriazine, 2,4-difluoro or 2,4- Dichloro-6-methoxytriazine, 2,4-difluoro or 2,4-dichloro-6-(β-methoxyethoxy)monotriazine, 2,4-difluoro or 2,4-dichloro-6-methylmercaptotriazine, 2,4 -difluoro or 2,.4-dichloro-6-phenylmer-triazine, and 2,4,6-trichloro or 2,4,6-trifluorotriazine. ? Particularly favorable monoazo dyes of formula (]) are K in formula (1)
,R,. X has the following meaning. That is, K is N-CI-, -alkylamino-still N, N・
-diCl'- 4-alkylaminobenzene residue, which can be substituted in its benzene ring by methyl, methoxy, chlorine, acedylamino, and each N-alkyl group independently of each other is hydroxyl ,
chlorine, cyano or phenyl), methoxybenzene residue (which can be substituted in its benzene ring by methyl),
Methoxynaphthalene residue, a. Minonaphthalene residues (which can be substituted by sulfo), hydroxynaphthalene residues (which can be substituted by sulfo), aminonaphthol residues (which can be substituted by sulfo in its naphthalene ring) and the amino group is substituted by methyl, α,β-dibromopionyl, α,β-dibromopionylaminobenzoyl or 2,6-difluoro-5-chloropyrimidylaminobenzoyl. ), 1-phenyl-3-methylpyrazolone residue (which can be substituted with methyl, ethyl, chlorine in its phenyl group), 1-phenyl-3-methylaminovirazole residue ( which can be substituted in its phenyl group by chlorine, sulfo), 2-
Methyl- or 2-phenylindole residue (which can be substituted by ethyl in the 1-position), N=methyl-yet N-ethyl-1.2,3.4
-tetrahydroquinoline residue or 1-chlorophenylamino-2-pentylnaphthoimidazole residue (which can be substituted in its naphthalene ring by hydroxyl, sulfo), R is hydrogen, chlorine, Methyl, trifluoromethyl, carboxyl, chloride-802-CI-2-, R5 is hydrogen or CI-3-alkyl, R6 can be substituted by hydrogen, hydroxyl or methoxy C1-6
-alkyl or cyclohexyl, and R7 means phenyl or chlorophenyl), and X means hydrogen, methyl, chlorine or ethoxy,
However, the group -N='N-'K is bonded to the phenyl ring at the ○1 position relative to the -S02 group, and K is 2
-amino-8-hydroxynaphthalene-6-sulfonic acid, R cannot be hydrogen or chlorine.

Particularly preferred monoazo dyes have the formula (1):
K is an N,N-diC1-4-alkylaminobenzene residue (which can be substituted in its benzene ring by methyl, methoxy, chlorine, acetylamino, and each N-argyl group can be substituted independently of each other by hydroxyl, chlorine, cyano or phenyl), 1-phenyl di-3-methylaminopyrazole residue (which can be substituted by chlorine, sulfo in its phenyl group) ) or 2-methyl or 2-phenylindole residues (which can be substituted by ethyl in the 1-position).

Furthermore, a monoazo dye represented by the following formula (2) is preferable.

In the formula, K1R1X has the meaning described above,
And R and the group N=N-K are 0 for the -SO2 group.
- or attached to the phenyl ring in the p-position.

Among the monoazo-dyed stings of formula (2), in formula (2), K gal-methynolyte 2-phenyl-intole residue, N,N-diethyl-3-acetylaminoaniline residue, N,'N -Siethyl-still N,N-dibutyl-3-methylaniline residue, N-ethyl-N-phenethyl-3-methylaniline residue, still 1-phenyl-3-
a methylaminopyrazole residue, X is hydrogen, chlorine or methyl, and R is hydrogen, chlorine, trifluoromethyl, ethylsulfonyl, p-chlorobenzoyl,
Sulfamoyl, N-methylsulfamoyl, NIN-
Dimethylsulfamoyl 4 N,N-diethylsulfamoyl, still N-methyl-N-cyclohexylsulfamoyl.

Also subject of the invention is a process for the preparation of monoazo dyes of the formula (1), which process is characterized in that the diazo component of the formula is diazotized and coupled to a coupling component of the formula H-K (4) . In addition, the formula (
K1R1x in 3) and (4) has the meaning described above in formula (1).

Diazotization of the diazo component of formula (3) is generally carried out by the action of nitrous acid in a low-temperature mineral acid aqueous solution, and coupling to the coupling component of formula (4) is carried out at an acidic, neutral or alkaline pll value. be done.

Optionally, after coupling, the free amino group in the group K can be converted into an acylamino or alkylamino group by means of an acylating agent or an alkylating agent.

Likewise, the hydroxyl group in radical K can be converted into an alkoxy group by alkylation.

The azo dye of the formula (]} containing a fiber-reactive group is the azo dye of the formula (3).
), a coupling component of formula (4) containing an acylatable amino group or a hydroxyl group,
and an acylating agent containing a fiber-reactive group are reacted with each other in any order.

As the coupling component containing an acylatable group, it is preferable to use a benzene-based or naphthalene-based coupling component.

a) X is k-bonded to the sulfophenyl ring at the p-position to the -8'02 group; b) R is 0- or p- to the =S''02 group?
is attached to the phenyl ring at the position, and
? c) One NH2 gas
A preferred method is to carry out the synthesis using a diazo moiety of formula (3) which is bonded to the phenyl ring at the p-position for one o2 group.

The azo-dyed sashimi of the ugly formula (1) is manufactured by oneself as follows. That is, R is hydrogen, . Chlorine, methyl, trifluoromethyl, carboxyl or -8.02-C1-2-alkyl, 7S. ,O,@-pendi-CO-R7 (where R5 is hydrogen or c1-3-alkyl R7 means phenyl or chlorophenyl); X means hydrogen, metal, chlorine or ethoxy. or N,N-di-4-alkylaminobenzene residue, which can be substituted in its benzene ring by methyl, methoxy, chlorine or acetylamino, and each N
- the alkyl radicals can be substituted independently of each other by hydrosil, chlorine, cyanochloride or Fuet-Loubet),
Methoxybenzene residues (which can be substituted by methyl on the benzene ring), methoxynaphthalene residues, aminonaphthalene residues (which can be substituted with sulfo), hydroxynaphthalene residues ( It can be substituted by sulfo; f:)), an aminonaphthol residue (which can be substituted by sulfo in its naphthalene ring,
So. The amino group is methyl, α,β-dibromopropionyl, α,β-dibromopropionyl 7-. 'Nobenzoyl can still be substituted by 2,6-difluoro-5-chloropyrimidylaminobenzoyl),
1-Fue Island Le 3-methylpyrazolone residue (this is so.
can be substituted with methyl, ethyl and chlorine in the phenyl group),! -7 Phenyl-3
One methylaminovira. zole residue (which can be substituted in its phenyl group by a base and an amorphous group), 2T methyl-T'! 4- or 2-phenylindole residue (which can be substituted by ethyl in the 1-position), N-methyl- or N-ethyl-1.2,3.4-7:trahy. Coupled to the coupling moiety of formula (4), which means a droquinoline residue or a 1-chlorophenylamino-2-pentylnaphthoimidazole residue, which can be substituted in its naphthalene ring by hydroxyl and sulfo. Manufactured by a cough ring. However, in this case, R in the diazo component is one NH2 group relative to one -SO2 group.
o bonded to the maenyl ring in the 1-position and 2-amino-8-hydro. If xinaphthalene-6-sulfonic acid is used, hydrogen cannot be chlorine.

In particular, in equation (4), K is N, N-Gc, -4-
Alkylaminobenzebi residues (which can be substituted in their benzene ring by methylhemethoxy, chlorine, acelylamino, and each N-alkyl group independently of each other can be substituted with hydroxyl, chloride, cyanochloride, etc.) or phenyl), ■-phenyl-3-methyl-aminopyrazole residue (which can be substituted in its phenyl group by chlorine or sulfo), or Preference is given to using a coupling component O, which also means a 2-methyl-yet 2-phenylindole group (which can be substituted in its 1-position by ethyl).Also as a diazo component It is particularly preferred to use a diazo component of the following formula (5).

(in the formula, R and X have the above meanings).

Particularly preferred monoazo dyes of the formula ( ]) are those in which X is hydrogen, chlorine or methyl and R is hydrogen, chlorine, trifluoromethyl, ethylsulfonyl, p-chlorobenzoyl, sulfamoyl, N-methylsulfamoyl, The diazo component of formula (5) which is N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl or N-methyl-Nlcyclohexylsulfamoyl is diazotized; and K
is a 2-methyl- or 2-phenylindole residue,
'N,N-diethyl-3-acetylaniline residue, N,
The coupling component of formula (4) is an N-diethyl- or N,N-dibutyl-3-methylaniline residue, an N-ethyl-N-phenethyl-3-methylaniline residue, or a 1-phenyl-3-methylaminovirazole residue. Manufactured by coupling.

Although a large number of coupling components can be used, specific examples include the following.

Aniline, dimethylaniline, diethylaniline, 3-
Methyl-dimethylaniline, 3-methyldibutylaniline, 3-methyl-diethylaniline, 3-acetylamino or 3-methoxyluponylamino-3-ureidodimethylaniline, 3-methyl-6-methoxydiethylaniline, 3-methyl-N-ethyl-N
-Butyl-aniline, 2,5-dimethoxydiethylaniline, N-ethyl-N-benzylaniline, N-ethyl-NL(β-cyanoethyl)-aniline, N-ethyl-N-(β-hydroxyethyl)-aniline, N-ethyl ethyl-NL-(β-acetoxyethyl)-aniline,
N,N-dibutylaniline, 3-acetylamino-N,
N-diethylaniline, N-methyl-N-(β-cyanoethyl)-aniline, 3-methyl-N,N-cy(β-
cyanoethyl)-aniline, 3-chloro-N,N-dimethylaniline, 3-methyl-N=ethyl-N-penzylaniline, 3-methyl-dipropylaniline, N,N-
di-n-propylaniline, 3-acetylamino-N,
N-C(β-hydroxyethynoyl)-aniline, 3-methyl-N,N-di(β-acetoxyethyl)-aniline, 31-methyl-N-ethyl-N-(3'-sulfobenzyl)-aniline, N-ethyl- N-(β-chloroethyl)-aniline, 2-methoxy-5-acetylamino-N-pendylaniline, 2-methoxy-5-acetylamino-N-(β-acetoxyethyl)-1N-pendylaniline, 3 -Methyl-N-ethyl-N=probylaniline, 3-methyl-N-ethyl-N-(β-cyanoethyl or β-hydroxyethyl)-aniline, 2
-Methyl-5-acetylamino-N,N-dimethylaniline, 2-chloro-5-acetylamino-N,N-dimethylaniline, 2-chloro-5-acetylamino-N~
(r-phenoxy-β-hydroxy-n-probyl)-aniline, 3-ureidoaniline, N-ethyl-N-(
β-hydroxyethyl)-aniline, N-ethyl-N-
(3'-sulfobenzyl)-aniline, 3-methyl-N
-presenting thiru-N-(β-sulfoethyl)-aniline, 3-
Penzoylamino-N,N-diethylaniline, 3-(
p-triloose sulfamoyl) 1N, N-di-engineering? Thylaniline, 3'(p-chloropenzoylamino)-N,N
-diethylnaniline, 3-methoxy-N,N-diethylaniline, 3-methyl-N,N-c(β-hydroxyethyl)-aniline, 3-methyl-6-methoxy-N,
N-(β-human oxyethylene')-aniline,
3-Achothylaminoaniline, 31-methyl-N-ethyl-N-phene≠luaniline, N,N-di-(β-cyanoethyl)-aniline, 3-acetyamino-N,N-di(β-cyanoethyl) -Aniline, 3-methyno-N-ethyl-N-(β-hydroethyl)-aniline, 3-methyl-N-ethyl 7N-(β▽cyanoethyl)
one aniline, N one (β-cyanoethyl) one aniline, .
N-methyl-N-bedozylaniline, phenol, 3-
Methylphenol, 3,4-dimethylphenol, 2-
Phenylphenol, 1-hydroxy-4-methoxybenzene, 1-hydroxy-4-tert-butylbenzene, 1-hydroxy-7-amino-3-sulfonaphthalene, 1-hydroxy-7-methylamino or -7-phenylamino-3- Sulfonaphthalene, 2-aminonaphthalene, 2-amino-6-sulfonaphthalene,
2-Amino-5-acetylaminomethylnaphthalene, β
-naphthol, 2-amino-5-methylaminosulfonylnaphthalene, 1-hydroxy-8-mono-3,6-
or -3,5-disulfonaphthalene, 1-hydroxy-8T-penzoylamino-3,6- or -3,5-
Disulfonaphthalene, 1-Hydroxy-8-ureido 3,6 di-or-Ray, 5-disulfonaphthalene, ↓. −
Hiroshita Roxy 8-acetylamino-3,6-Madaha 73
．． 5-disulfonaphthalene, j7. (3',-chlorophenyl)-3=methylpyrazol-5-one, 1.7<
2'-nichloro-6'-methylphenyl)-3-methylbilazonyl-5-one, 1-phetonyl-3-methylpyrazol-5-one, 1-. (2'.3' one or 4'-
sulfophenyl)-3-methylpyrazol-5-one,
1-(2〆1chloro-47- or 5'-sulfophenyl)=3-ylpyrazol-5-one, 11. (3'
One still is 4'-α,β-dibromoprobio-ruamino)-benzoylamino-$-hydroxy-3. 5 =
'il: 4,6-disulfonaphthalene, 2-α,β
-Dibromoprobionylamide-8-hydroxy-6-
Sulfonaphthalene, 3-α,β-dibromoprobionylumemethylamino-T8-hydroxy-6-sulfonaphthalene, 1-[Tei/. − (. 2 //, 5“
-difluoro or "-chloropyrimidylamino)-benzoylamino]-8-hydroxy-4,6-disulfonaphthalene, 1-(2'-methyl-47-sulfophenyl).-3-methylpyrazole-5 -on, l.-(4'
,8'-disulfonaphth-2-yl]-3-methylvirazol-5-one, 1-C5',7'-disulfonaphth-2-yl]-3-methylpyrazol-5-one, 1
-(2.'-chloro5'-sulfophenyl)-3-
Methyl. 5-Aminopyranol, 1-,(2'-chloro4'-sulfophenyl)-3-ythyl. =5-aminopyrazole, 1-(3' or 4'-sulfophenyl)-3-methyl-5-aminovirazole, 2-methylin. Dole, 2-phenylindole, 1-methyl? -phenylindole, 1-octyl? -Methylindole, N-methyl-N,N-diphenylamine, acetoacetanilide, 1-(4'-monomethylphenyl)
-3-methylbi. Razol=5-one, 1-ethyl-2
-methylindole, 1-phenyl-3-methyl-5-
Aminovirazono murmur 1-Hydro husband sinaphthalin, 1-
Hydroxy-4-sulfonaphthalene, 1-(2'-chlorophenylamino)-9-hydroxy-? -Methyl-I
H-naphtho(1.2=d.) imidazole-7-sulfonic acid, 1-(2'-chlorophenylamino)-9-hydroxy-2-1-h-naphtho(1.2-d.) imidazole-7-sulfone acid, 1-(2-methyl-6-
chlorophenyl)-3-methyl 1razole T5 one,
N-methyl-also (.maN-ethyl-1,2,3,4-
Tetra-bank droquinoline.

The present invention is particularly applicable to the following formula (3) which is used as a diazo component.
) is also concerned. In the formula, R is hydrogen, halogen, CI-6 7-alkyl, trifluoromethyl, carboxyl or -SO2 Cl-6
-Alkyl, -S02- Rl1 group (wherein R1 is a substituted or unsubstituted benzyl group, a phenethyl group or a naphthylmethylene group, R2 and R3 are each independently hydrogen,
C1-6-alkyl is C5-'y-cycloalkyl, and R4 is unsubstituted phenyl group or halogen, C
, -4-alkyl or Ct-4-alkoxy) and X means hydrogen, CI-4-alkyl, CI-4-alkoxy or halogen, However, R and X are N
If one H2 group is attached to the phenyl ring in the ○1 position relative to one -SO2 group, it cannot be hydrogen or chlorine or methyl in the p-position relative to two -SOz groups.

Preferably, a) X is bonded to the sulfophenyl ring in the p-position relative to one -802 group; b) R is bonded to the phenyl ring in the 0- or p-position relative to one SOZ group; and c) a compound of formula (3) in which one NHz group is bonded to the phenyl ring in the 0- or p-position relative to the -so2 group.

It is particularly preferred that R is hydrogen, chlorine, methyl, trifluoromethyl, carboxyl or -802-CI-2-
alkyl, one 802-ben-Co-R7 group (where R
5 is hydrogen or C1-3-alkyl, R6 can be substituted with hydrogen, hydroxyl or methoxy CI
-6-alkyl or cyclohexyl, and R7 means phenyl or chlorophenyl);
and X means hydrogen, methyl, chlorine or ethoxy, and R and X are Alternatively, it is a compound of formula (3) which cannot be chlorine or methyl at the p-position relative to one S02 group. Particularly preferred are compounds of the following formula (5): (wherein R and X have the meanings given above).

The compound of formula (3) is produced by the following method.

That is, a compound of the following formula (6) (wherein 'Hal means halogen and R has the meaning described in formula (3) Vr.) is converted to a compound of the following formula (7) (wherein, X is the formula (3) has the meaning stated in
and sulfonate the reaction product,
Then, that NO2 group is reduced to an amino group.

The compounds of formulas (6) and (7) above are known per se and can be prepared by known methods. can be obtained by

X is hydrogen or halogen, and the group R (wherein R2 and R3 are
7-cycloalkyl) is a compound of formula (3), which is a compound of the following formula (8) (wherein, Ha+ means halogen), t, x
is hydrogen or halogen, the reaction product is converted into a sulfonic acid halogen compound, and then sulfonated, and the following formula (9) (in which .R2 and R3 has the meaning given above) with the amine, and then ? It can be obtained by a modified method in which one NO2 group is reduced to an amino group.

The method for producing the compound of formula (3) can be carried out in a known manner. The reaction is carried out at temperatures between 0 and 150C, optionally under pressure, between 7 and 150C. 10 pl1 range. It is carried out in an aqueous solution or an organic solvent mixture, such as a mixture of acetone and water. The reduction of the nitro group is likewise carried out in a manner known per se in the presence of iron powder in glacial acetic acid. Sulfonic acid oath. can be introduced by a known method, for example, at a temperature of
Unable to carry out in 5% oleum.

The reaction for converting the reaction product of the compounds of formulas (8) and (7) into a sulfonic acid halide, especially a sulfocylate, is carried out by a known method by converting the sulfonic acid in an organic medium such as sulfonic acid or acetonitrile. It is carried out by reacting with phosphorus oxychloride.

Examples of the starting compound of formula (6) include the following: 4-chloro-3-nitrophenylethylsulfone, 4-
Chloro-3-tritrobenzene-1-sulfamide, 4-
Chloro-3-tritrobenzoic acid amide, ■,2-dichloro-3-nitrobenzene, 4,4'-dichloro-3-nitrobenzophenone, p-nitrobenzene, 1,4
-Dichloro-2-nitrobenzene, 0-nitrochlorobenzene, 4-chloro-3-nitrobenzenesulfonic acid-
N,N-dimethylamide, 4-chloro-3-nitrobenzene-1-sulfonic acid-N-methylamide, 4-chloro-3-nitrobenzene-1-sulfonic acid-N',N-diethylamide, 4- Chloro-3-nitrobenzene-1-
Sulfonic acid -N-ethyl, -propyl, -isopropyl, -butyl, -butyl, -isobutyl, '-, tart-butyl, -pentyl-, -hexynolyl or sulfonic acid. Chlorohexylamide, 4-chloro-3-nitrobenzene'' 1-N-methyl sulfonate←N-cyclohexylamide, 4-chloro3. ．．
．． - Is it Trovedezen? -7,,*Acid-N-β? one.
,．． ? Wear,, one. -β-methoxy amino, 4-chloro-3. - Nitrobe. Nzen-1--N-methyl sulfonate-N-β-hydroxydiethylamide, 4-nichloro-3-ditrobenzoate--N-methyl-sulfonic acid--1-N-methyl ethyl, 1 p? Robyru- or mono-butyruamide, 4-chloro-3-2-ditorobenzoic acid-N=, dimethyl-, 1-ethyl-, 1-butyl-butyl-amide, 4-chloro-3-2-ditorobenzoic acid-N= Methyl-N-cyclohexylamide, 4-chloro-3-nitrophenylbenzyl sulfone, 4-chloro-3-nitrophenylbenzyl sulfone, 4-kp. Low. 3-nitropenzophenone, 4-chloro-3-tritro-1-trifluoromethylbenzene, 4-chloro-3-ditrotoluene, 4-chloro-3? 13 Torobenzoic acid. ．．・．．
- As starting materials for formula (7), benzene-subsulfuric acid,
Examples include 4-methylbenzenesulfinic acid, 4-ethoxybenzenesulfinic acid, and 4-chlorobenzenesulfinic acid.

Examples of the starting material for formula (8) include 4-chloro-3-ditrobenzenesulfonic acid and 2-chloro-5-ditrobenzenesulfonic acid.
- Examples of starting materials for formula (9) include ammonia, dimethylamine, methylamine, diethylamine ethylamine, probylamine, and N-methyl-N-cyclohexylamine.

Examples of compounds of formula (3) include: 2-amino-4-ethylsulfonyl-1,1'-diphenylsulfone-3'-sulfonic acid, 2-amino-4'-
Chloro-4-ethylsulfone-1,1'-diphenylsulfone-3'-sulfonic acid, 2-amino-4l-methyl-4-sulfonic acid amide 1,1'-diphenylsulfone-37-sulfonic acid, 2-amino 4'-methyl-4
-carboxamide-1,1. ' -diphenylsulfone-37-sulfonic acid, 2-amino-4' -methyl-
6-chloro1,1'-diphenylsulfone-31 monosulfonic acid, 2-amino-4'-methyl-4-p-chloropenzoyl-1:,? 1'-diphenyl sulfone-3'
-sulfonic acid, 4-niamino-47-methyl-II 1'
-diphenylsulfone-3'-sulfonic acid, 2-amino-4'-methyl-4-chloro-1,1'-diphenylsulfone-3'-sulfonic acid, 2-amino-4'-chloro-1,1'- ? Diphenylsulfone-3'-sulfonic acid, 2-amino-4'-methyl-4-(-sulfonic acid-
N,N-dimethyl, one ethyl, one propyl, one isopropyl butylamide)-1,”.1
"-diphenylsulfone-3l-subsulfonic acid, 2-amino-4'-methyl-4'-chloro-4-
(Sulfonic acid? 1N-methyl, 1ethyl, 1β-bidro?xyethyl, 1β-methoxyethyl, 1propyl, 1isoprobyl, 1butyl, 1S1butyl, 1i?sobutyl, -tert-petit) C, one pentyl, one hexyl or -cyclohexylamide) l-11,. 1-diphenyl sulfone-31-
Sulfonic acid, 2-amino-4-(N-methyl sulfonate, monoethyl, monopropyl, monopropyl, monobutyl, monobutyl, monoisobutyl, -ter
t-Butyl-, monopentyl-, monohexyl- or -cyclohexylamide)-1.1'-diphenylsulfone-3'-sulfonic acid, 2-amino-4-(sulfonic acid-N-methyl-N-cyclohexylamide) =1.1
'-Diphenylsulfone-31-sulfonic acid, 2-amino-4/-% thi-4-(sulfonic acid-N-methyl-N-cyclohexylamide). -1.1'-diphenylsulfone-3'~sulfonic acid, 2-amino-4-carpoxyamide-1.1'-diphenylsulfone-3'
-sulfonic acid, 2-amino-4'-methyl- or-
4'-chloro-4-methyl-, monoethyl- or -benzylsulfone-i,i'-diphenylsulfone-31
-sulfonic acid, 2-amino-4' -chloro or -
4'-Methyl-4-penzoyl or -4-p-chloropenzoyl-1,1'-diphenylsulfone-37
-sulfonic acid, 2-amino-4'-monomethyl-neck or -4
'-Chloro-4-trifluoromethyl-1,1'-diphenylsulfone-37-sulfonic acid, 2-amino-4,
4'-dichloro-1,1'-diphenylsulfone-
3'-sulfonic acid, 2-amino-4l-methyl-4-carpoxy-1,1'-diphenylsulfone-3'-sulfonic acid, 2-amino-4,4'-dimethyl-1,1'
-Diphenyl sulfone-3. '-sulfonic acid, 2-amino-4-. Trifluoromethyl-i,i' monodiphenylsulfone-37-sulfonic acid.

The material of formula (1) according to the invention may be in the form of the free sulfonic acid or its salts, but is preferably in the form of a fence.

Suitable salts are, for example, alkali metal salts, alkaline earth metal salts, ammonium salts or salts of organic amines. Examples include the sodium, lithium, potassium, ammonium or triethanolamine salts.

The dyes of formula (1) are suitable for dyeing and printing materials containing amide groups, such as fiber yarns, fiber fabrics etc. made of wool, silk and polyurethane fibers, but in particular for dyeing and printing synthetic polyamides. It is particularly suitable for

In this case, customary dyeing methods can be used and level dyeings are obtained. - The dye according to the present invention - exhibits excellent brightness and color density, good exhaustion properties, and very good build-up properties. Is the dye fast? The properties are generally good, including friction fastness, acid and alkali fastness, wet fastness, especially wash fastness, water fastness, hot water fastness and sweat fastness. Particular praise should be given to its very good light fastness and extremely high stability towards bomaldehyde. ? Examples for explaining the present invention are shown below. Parts in the examples are parts by weight. The relationship between parts by weight and parts by volume is the same as the relationship between grams and cubic centimeters. 'RF values were determined by thin layer chromatography on silica gel plates. 5 parts of ethyl acetate,
A developing solution of 5 parts of chloroform and 4 parts of methanol was used.

Example 1 Moist 4-chloro-3-nitrophenyl ethyl sulfone (purity: 50.2%) 149.12% 4-chlorobenzenesulfinate sodium salt (purity: 68,
8%)? 8 6. 7 f? and 150 parts each of methanol and dimethyl sulfoxide.
Stir at ~72°C for 5 hours. Product by r at room temperature? washed with methanol and water and dried in a vacuum chamber at a temperature of 60-70°C. Melt? Point 215-218°C.
11 1 0 9 t' of the obtained compound is 25 - fuming?
The mixture is placed in sulfuric acid at a temperature of 65 to 6...8°C for about 5 hours. The precipitate precipitated by cooling on ice is P
The mixture is filtered, stirred in water, and dissolved to a pH of 7 with concentrated sodium hydroxide solution. After adding salt, apply suction. The wet P filter cake is placed in 200° water containing 502° iron powder and 3° glacial acetic acid and stirred for 20 minutes at boiling temperature. After carefully adding 5 tons of sodium carbonate, P is separated from the iron powder? do. This e-liquid was diluted with a concentrated salt solution, and the resulting precipitate was filtered and washed with a salt solution. , and 60
Vacuum drying at 70U'? A light gray powder 1021 having the structural formula shown above is obtained. RF = "0. 4 4 2 Example 2' 4-Chloro-3-nitrobenzene-1-sulfamide 7
0.95f, toluene-4-sulfinic acid sodium salt (purity: 95.6%) 5 8. 6 5 9 and calcined sodium acetate 12.32 total dimethyl sulfoxide 1. Stir in 50 ml at a temperature of 40-45° C. for 2.5 hours.

Add this mixture to 375 ml2 of alcohol and 750 ml of water.
m. and filter the precipitated product with suction f. The filter cake is washed with warm water and dried under vacuum at a temperature of 60-70°C. Melting point: 181-185°C.

The resulting compound 1017 was dissolved in 25% fuming sulfuric acid 2757.
and stir the resulting solution for 4 hours. The sulfo product is then precipitated by pouring onto ice and adding sodium chloride, filtering and washing with sodium chloride solution.

Add 401 parts of iron powder and 4 parts of glacial acetic acid to the moist, unfiltered cake.
The mixture was placed in 400 tne of water containing nrl and reduced at boiling temperature for 20 minutes.

After careful addition of 60 g of a 1 molar solution of sodium carbonate, the iron powder is removed by filtration, and common salt is added to precipitate the formed amine.

This is filtered, dried and purified by chromatography.
Compound 1o3 of the above structural formula. 'iy is obtained. R
F-0. '3 3 3 Example 3 4-chloro-3-nitrobenzoic acid (purity: '98) 6
1.8F, toluene-4-sulfinic acid (purity: 89.
3%) 6 5, 9g and power calcined sodium acetate 24
．． 6 in dimethyl sulfoxide 150 me
Heat to 115°C while stirring. After 1 hour, the reaction mixture was poured into cold water and ? Then adjust to Congo Red acidity with concentrated hydrochloric acid. The residue after P filtering and washing with water is 60~
Vacuum dry at a temperature of 75°C. This makes the powder 94.5
Get 2.

72. of the obtained compound. ir7, chloroform 300-
21.7fnt. of thionyl chloride at boiling temperature in a mixture of 21.7 fnt. It is converted to carboxylic acid chloride by reacting with Petroleum ether 3 in clear solution
0 0 tne was added, and the resulting precipitate was separated from P.
Dry briefly. This gives 72.87 silicate chloride. Melting point: 162'-164°C. 37 of this acid chloride
．． 4F was added to 100 ml of concentrated ammonia solution and stirred at room temperature for 3 hours. The generated amide tF is filtered, washed with water, and dried under vacuum at 60-70°C. This gives powder 35f with a melting point of 227-230°C. 3 of this amide. 8, ? f Sulfonate in 90ml of fuming sulfuric acid at room temperature for 25 hours. Pour the solution onto ice and precipitate the product by adding potassium chloride. After drying, a gray powder is obtained from the precipitate which has been filtered and washed with a saline solution. 6. '
8 iP is obtained.

The obtained nitro compound 45.8F is poured into 200 ml of water containing 20 f' of iron powder and 2 ml of glacial acetic acid, and stirred at boiling temperature for 15 minutes. After careful addition of 30 molar solution of sodium carbonate, iron residues are removed by filtration. The product of the above structural formula is precipitated by adding common salt and filtered.

The filtration residue is washed with a saline solution and dried under vacuum at a temperature of 60-70°C. However, as. 7"y of the desired product is obtained.RF=-o.2osExample 4'1.2-dichloro-3-nito-1benzene5'7.
6 f and toluene-4-sulfinate sodium salt (
Purity: 9 5. 6) 55.8F and 65-70℃
dimethyl sulfoxide 150tnI1! In it, stir with a whisk, a yellow salt-containing solution is produced. 1 in this solution
Add 50 rne of alcohol and 500 ml of water. The precipitate was filtered and washed at 60-70°C. Dry in vacuum.

Since a powder of 81.3S' with a melting point of 132-138°C is obtained, 80.2ri of oleum (25%) of this powder is obtained.
) Sulfonate in 2 0 6 tnl Pour onto ice, filter off the precipitate and neutralize with concentrated sodium hydroxide solution in water. The precipitate is filtered off with suction and dried under vacuum at 60-70°C, yielding 99.3 g of product.

The obtained nitro product was added to 300 ml of water containing 501 ml of iron powder, 3-glacial acetic acid, and stirred at boiling temperature for 30 minutes. After carefully dispersing 4.7 ft of sodium carbonate, remove residual iron by filtration. The desired product having the above structural formula is added with salt and precipitated. The desired product is isolated in chromatographically pure form by filtration and vacuum drying at 60-709 F. The yield is 96.7 F. RF. ．． ．． = ,0. 3 6 5 Example 5- 4-Chloro 73 Nitrobenzoic acid 2 0 1. 52 is converted to the carboxylic acid chloride by reaction in 600 ml of chlorobenzene containing 100 ml of thionyl chloride and a catalytic amount of dimethylformamide. The resulting solution was concentrated to 400ml, and aluminum chloride 17.5r
i and slowly heat to 75°C until hydrochloric acid gas stops evolving. Carefully add ice-cold water and concentrated hydrochloric acid;
．． The organic phase is separated and washed thoroughly with water and sodium carbonate solution. After evaporation of the solvent, the residue is recrystallized from methanol. The desired product 92 has the neat structure shown above. '
Jf is obtained. 11NF=0.4. 6 8 Example 6 p-Nitrochlorobe? Zen 6 8. 0p F and toluene-4-sulfinate sodium salt (purity: 89.3%
) 107.51 and diitylsulfoxide 1457! The mixture was stirred in a bowl to make it homogeneous, then it was dissolved and kept at 80°C for 8 hours.

Then, add water, precipitate, filter through +F, wash with water, and vacuum dry at 60-70°C. By hardening, the melting point is 16
Powder between 1 and 167℃! ．． 1. 1. 6y is obtained. 1 of this compound 10. ．． 4. ' f i 2 5
Sulfonate in 336% of fuming sulfuric acid at room temperature for 4 and a half hours, and precipitate the product by pouring onto ice and adding common salt. The resulting precipitate is filtered and washed with saline solution. After drying 26 7. 5 f powder debris melting point is 83-85
183 g of the compound at .degree. C. are obtained. ．． Atoluene-4 = sodium sulfinate salt (purity: 92, 7%) 7. ．． ! It is converted into a sulfone derivative by reacting with r. The product is poured into a bottle and the precipitated product is filtered, washed and dried under vacuum at 60-70°C. Melting point 19. 1 7 1 9. Since the compound at 4°C is obtained: 103fffi of this compound
Fuming acid rest (25%), 2! 1 Sulfonate in 5 steps.

Pour into water to precipitate the product, P filter, wash, and 6
0-70p. Dry in vacuum. 1. of the obtained nitro compound.
2. 5 iP 'i iron powder 4 0 f. and glacial acetic acid 4-
．． The mixture was poured into 400ml of water and stirred at boiling temperature for 30 minutes. After careful addition of 5.2 liters of sodium carbonate, the iron powder ff:P is removed. Cool P liquid! The precipitated product is filtered through TiF, washed and dried under vacuum at 60-70°C.

A pure product can be obtained by chromatographic analysis.

5. 260.4y of the obtained nitro compound was mixed with water containing 802 iron powder and 5 ml of glacial acetic acid. ．． ．． Pour into 10 ml of water and reflux at boiling temperature for 30 minutes. Avoid sodium carbonate in 852. After heavy addition, the iron powder is separated by p. :f
Is it because precipitation occurs when concentrated hydrochloric acid is added to I-liquid? , the precipitate is washed with water and dried at 60-70°C. Compounds 114 and 31 having the above structural formulas are thus obtained. t=0.2M' Example 7 2-Nitrodiphenylsulfone-4-sulfonic acid sodium salt 36. sulfolane '50 at a temperature of 68-72°C to induce '5f into sulfonic acid chloride.
React with phosphorous chloride 36,51 in a mixture of 50 tne and acetonitrile. The reaction mixture is poured into ice-cold water to precipitate the product, the precipitate is filtered, washed with water until neutral, and dried over P20. A compound having a melting point of 157-159°C is obtained.
' 29.81 of the acid chloride obtained above was mixed with 58 of fuming sulfuric acid.
fnl and sulfonated at 20-37°C for 25 hours. Pour onto ice and add common salt to precipitate the product,
The precipitate is filtered and washed with saline solution until neutral.

It is converted to the amide in 5 ml of concentrated ammonia l2' at 0-5[deg.]C, filtered and washed with saline solution.

Add 15 g of wet filter cake iron powder and 1. glacial acetic acid. 5
ml of water and stirred for 20 minutes at boiling temperature. After carefully adding 2.71 ml of sodium carbonate, remove the remaining iron without removing too much. Add all the chloride to precipitate the product, filter it, and after washing 6 o~
Vacuum dry at 70°C. basket? = '0. 2 9 7F Example 8? ? Compound obtained in Example 2 (purity 66.6%) 6.12
40 g of water, 10 g of ice and 2 g of concentrated hydrochloric acid. Pour into the mixture with 5 ml and stir. The mixture was heated to 10 to 18°C and diazotized with 94N sodium nitrite. After it has stale, the slight excess of nitrite is decomposed with total sulfamic acid.

Separately, add 1.632 parts of N to 1.5 parts of water and 1.5 parts of concentrated hydrochloric acid.
.
and inject it into the above suspension of diasonium. Add 2N sodium hydroxide solution to p
11 to 3.5 and remove the precipitated dye through a Δ1 sieve. This is placed in f 100 ml of water, 2 nm constant sodium hydroxide solution is added to dissolve under alkaline conditions, and salt is added to precipitate the dye again. Dyeing by filtration and washing with salt solution at 60-70℃
Dry in vacuum.

However, dye 5. 15 f was obtained, and when polyamide material was dyed with this in a weakly acidic dye bath, it turned bright red. dyed in color. This dye had very good Nil photofastness of the dyeing, and also had good stability to formaldehyde and wet fastness. λm,
x-51'7nm Example 9 88i▼ 2-Amino-4 produced according to Examples 1 to 7 above
-Chlorodiphenylsulfone-47-methyl-37-
Sulfone V, 80 ml of water, 201 ml of ice, and 51 ml of concentrated hydrochloric acid
Stir in a mixture with nl and diisolate with 4N sodium nitrite 5- at a temperature of 8 to 14°C.

After some time, the slight excess of nitrite is destroyed with sulfamine biao. 2-methylindole in 5 ml of concentrated hydrochloric acid2.
6 2 9 solution was added dropwise and diluted with sodium acetate.
) Buffer II4 to complete the coupling. The dye is filtered hot, washed with water and vacuum dried at a temperature of 60-70°C. However, dye 8. 651i' is obtained. This dye is highly soluble in water with added sodium carbonate.

The polyamide material was dyed a bright reddish yellow color from a mildly acidic dyebath. This dye has very good color fastness, particularly light fastness and acid stability, and also has high wet fastness. λ = 410 nm. ．． l:m
aX Example 10 2-Amino-4-chlorodiphenylsulfone-47-methyl-37-sulfonic acid is diazotized in the same manner as in Example 9. Next, 30 nt of water and 2.0 nt of concentrated hydrochloric acid were added to this diazo solution. A solution of 3-methyl-1-phenyl-5-virazolimine of 3,59f in a mixture with 5 ml is added and the coupling is allowed to take place at room temperature. P-filtered dye f 1 0 0 rnl taken into water p1{7
Add and dissolve 2N solution until . After this, salt is added to precipitate the dye again. The precipitate is vacuum-dried at 60-70°C.

As a result, 9. A dye of 35 r was obtained, which dyed polyamide material bright yellow from a weakly acidic dyebath. Very high light fastnesses, good stability against Heylemaldehyde 1 and wet fastnesses were achieved with this dye. λ = 4 1 8 nmmaX Example 11 2-Amino-1-kurodiphenylsulfone-4'-methyl-3'-sulfonic acid 7.2 in the same manner as in Example 9
39f' Diazotize.

Then, add N,N-diethyl-m- to this diazo solution.
Toluidine 3. A solution of 2 6 F in hydrochloric acid is added and sodium iate is added to complete the coupling.

P.7 Add the dye dissolved in water to salt. in. Precipitate, filter with suction and dry under vacuum at 60-70°C.

Thus, 8.82 dyes were obtained. When polyamide fibers were dyed with this dye in a weakly acidic bath, they were dyed bright red. The dye shows excellent build-up properties, the light fastness of the dyeing is very good, and the stability to formaldehyde and wet fastness are also very good.

λmax=507nm speed 3jl section? 2-Amino-4'- produced according to Examples 1 to 7
Chlorodi7enyl sulfonic acid (purity 85.4%) 8. "1',.4. iP water] 50-
and 5 rrt of concentrated hydrochloric acid.
Diazotize with 5 ml of 4N sodium nitrite at a temperature of °C. After stirring the resulting suspension for a while, a small excess of nitrite is destroyed with sulfamino acids. 2627 2-methylinzole dissolved in concentrated hydrochloric acid was added dropwise,
Coupling at room temperature:. Suction r the dyed sting
Dissolve in r 7 warm water and add potassium chloride to salt out. The precipitate is filtered out, washed, and 60~7. 0℃
Dry in vacuum. However, the target dye c+. c+sy4
It's a good deal.

When this dye was used to dye a polyamide material in a weakly acidic bath, it was dyed yellow with a bright reddish tinge. The dye exhibits excellent external fastness, good acid stability, formaldehyde resistance and wet fastness. λ=402
nmmax,, Example 13 2-amino-6-dimethylamidesulfone-47-methyl-diphenylsulfone-37-sulfonic acid (purity: 75.2%) 1 produced according to Examples 1 to 7
1.54f, 70me of water and 5m7 of concentrated hydrochloric acid! and diazotized with sodium nitrite at a temperature of 25-28°C. After some time, the small excess of nitrite is destroyed with sulfamic acid.

Add 3-α,β-dibromopionylaminobenzoyl-K-acid (purity: 5) to 100 ml of water at pH 7.
5. 1%)23. ．． 66F and cooled to 2°C. This is added dropwise to the diazo suspension and kept at its plI'k7 with sodium hydroxide solution. The resulting dye was salted out with potassium chloride, filtered with suction, and
Vacuum dry at a temperature of ~70°C. Therefore, the structure of the above structural formula 18. 7 1 f is obtained. λ = 5
02nmmax In the same manner as in Examples 1 to 13 above, except that a compound of the following formula (wherein R and X have the meanings listed in the table below) was used as the diazo component. Used and cutlet. Using the compounds shown in the table below as pulling components, valuable dyes can be obtained in the same manner as above. It was done. These dyes have the same good properties as those mentioned above, and each dyes the polyamide oten and wool in the shades described in the table.

Shie,,,)Yuta. vinegar. ? ．． It was obtained by etherifying the hydroxyl group after coupling the 8 compounds with each other.

The procedure was carried out in the same manner as in Examples 1 to 13, except that the following formula was used as the diazo component. (wherein R and X have the meanings listed in Table 2 below), and. Table 2 below as coupling components
Using the compound shown in Figure 1, valuable dyes were obtained similar to those described above. These dyes have similar excellent properties to those mentioned above and dye polyamides and wool in the colors listed.

In the same manner as in Examples 1 to 13, except that the compound of the following formula (in the formula, R and X have the meanings listed in Table 3 below) was used as the diazo component, and the compounds shown in Table 3 were used as coupling components Using the compounds, valuable dyes similar to those described above were obtained.

These dyes have the same excellent properties as those mentioned above and dye polyamides and wool in the colors indicated in the table.

In the same manner as in Examples 1 to 13, except that a compound of the following formula (wherein R and X have the meanings given in Table 4) was used as the diaso component, and as a coupling component
Using all of the compounds listed above, valuable dyes similar to those described above were obtained.

These dyes have the same excellent properties as those listed above and dye polyamides and wool in the colors listed.

In the same manner as in Examples 1 to 13 above, however, the cyazo component is expressed by the following formula (wherein, X and 2 have the meanings listed in Table 5 below).
Valuable dyes similar to those described above were obtained using all the compounds listed in Table 5 as coupling components.

These dyes have the same excellent properties as those described above and dye polyamides and wool in the colors shown in the table below.

Dyeing example ■ 500 parts of an aqueous dye bath containing 22/t ammonium acetate and adjusted to pll 5 with acetic acid was prepared to produce Helanca (trade name) tricot fabric 1
0 parts were dyed with this dyebath.

As the dye, the dye obtained in Example 12 was used in an amount of 1% based on the weight of the object to be dyed. Staining time is 98℃
The temperature was 30 to 90 minutes. The dyed Helanka fabric was taken out of the dye bath, washed and dried in a conventional manner.

A reddish-yellow dyed Helanka fabric with a bright color and generally good dye fastness was obtained.

Dyeing Example ■ An aqueous dyebath containing monosodium phosphate lr1f/t and adjusted to p■6 with disodium phosphate was prepared, and 10 parts of Herlan force tricot fabric were dyed in 500 parts of this aqueous dyebath.Dye. The dye obtained in Example 11 was used in an amount of 2% based on the weight of the object to be dyed.

The staining time was 30 to 90 minutes at a temperature of 98°C.

The dyed Helanka fabric was removed from the dye bath, washed and dried in the usual manner.

A red-dyed Helanka fabric with a bright color and generally good dye fastness was obtained.

Dyeing example■ 10 parts of the wool fiber fabric were dyed in a total aqueous bath of 500 parts.

The aqueous bath contains, based on the total weight of the fibers, 4 parts by weight of ammonium sulfate, 1.5 parts by weight of 80 thiacetic acid, 1 part by weight of substituted alkylamino polyglycol ether, and 3 parts by weight of the dye according to Example 13. It had been. Dyeing time is 9
The temperature was 8°C for 30 to 90 minutes.

The temperature was then lowered to 80°C, neutralized by the addition of 2.5wt of 25w aqueous ammonia, and held at this temperature for 15 minutes to complete the dyeing. The dyed wool fabric was removed from the dye bath, washed and dried in the usual manner. As a result, a wool dyed material with a bright color and excellent dyeing fastness was obtained.

Claims (1)

[Claims] 1 Formula. [Wherein, K is an amino or alkoxybenzene residue, an amino or alkoxynaphthalene residue, a naphthol residue, an aminonaphthol residue, a pyrazolone residue, ? means a residue of aminovirazole, a residue of indole, a residue of naphthoimidazole, a residue of diphenylamine, a residue of tetrahydroquinoline, or a residue of acetoacetamide, which groups may be further substituted. Yes, R is hydrogen, halogen, C1i6-alkyl, trifluoromethyl, carboxyl or -SO? 1CI'-
6-alkyl, -802-J, (where R is substituted or unsubstituted phenyl or naphthyl?σ1
-4-alkyl group, R2 and R3 are each independently hydrogen or substituted or unsubstituted 01-6-alkyl group or C5-7-cycloalkyl group, and R4 is substituted or unsubstituted phenyl group. meaning). means,
．． and. X means hydrogen, C1-4-alkyl, CI4-alkoxy, or halogen, provided that the group -N=N-K
Ga-SOm? Feni at 〇1 position for one unit. bond to the ring. and K is the residue of aminonaphthalene sulfonamide or 2-ami. The residue of 8-hydroxynaphthalene'-6-sulfonic acid has the formula (1
) is hydrogen or salt wood... Impossible! ] wood, azo dye. ．． ．． 2 'Xga-8 02 ""
is bonded to the zulfophenyl ring at the p-position relative to the "' group, and K1R, The monoazo dye described in item 1. 3. The length is 0- or p-1 to the ?-802 group, and the monoazo dye is bonded to the pthyl ring at the 0- or p-position, and K,,R,X
Claim ratio 2. has the meaning stated in claim 2. Monoazorei as described in section. 4 group 1N=N-+K is bonded to the phenyl ring at the 01 or p-1 position relative to the -8',02.1 group, and K. R,'X? The monoazo dye according to claim 3, which has the meaning set forth in claim 3. 5 K is N-C, -4-alkylamino or N,
N-di-CI-4-alkylaminobenzene residue (
It can be substituted in its benzene ring by methyl, methoxy, chlorine, acetylamino, and? Do・1.・Each N-alkyl group can be independently substituted with hydroxyl, chlorine, cyano moiety or phenyl), methoxybenzene residue (which can be substituted with methyl on its benzene ring) (can do 4 things)
Methoxynaphthalene residue, aminonaphthalene. groups (which can be positively substituted by sulfo), hydroxynaphthalene residues (which can be positively substituted by sulfo), amino phthol residues (which can be substituted by sulfo), can be substituted by Kurubo on its naphtha'non ring, and its amino group can be substituted with methyl, α
, β-dibromop-2, α,β-dibromo-bionylaminobenzoyl or 2,6-difluoro-5-chloropyrimidylaminobenzoyl), 1- phenyl-3-methylpyrasolone residue (which can be substituted in its phenyl group by methyl, ethyl, chlorine), 1-phenyl-3-methylamino virazole residue (which can be substituted in its phenyl group by methyl, ethyl, chlorine), 2-methyl di- or 2-phenylindole residue (which can be substituted with ethyl in the 1-1 position) ), N-methyl or N-ethyl'1',2'',3,4-tetrahydrogynoline residue or 1-crophenylamitri-2-pentylnaphthoimidazole residue (this is the naphthalene ring R is hydrogen, chlorine, methyl, trifluoromethyl, carboxyl, and light is -SO2-CB-2=alkyl', -8
02-Benzyl?・-Co-Ih group (where,
R6 is hydrogen or CI-3-alkyl, R6. is hydrogen,
auto-6-alkyl which can be substituted by hydroxyl or methoxy is cyclohexyl and R7 means phenyl or chlorophenyl. ), and X is hydrogen, methyl, chlorine or ethoxy, provided that the group -N=N-K is bonded to the phenyl ring in the ○1 position relative to the -so2- group and K is 2-amino8
- R cannot be hydrogen or chlorine when it is the residue of hydroxynaphthalene-6-sulfonic acid, as stated in claim 4? Monoazo dye listed above. 6 K is N,N-cy-4-alkylami. Novenzene residues (which can be substituted in their benzene ring by methyl, methoxy, chlorine, acetylamino, and each N-argyl group independently of each other can be substituted with heptadroxyl, chlorine, cyano, etc.) can be substituted by phenyl), 1-phenyl-3-methylaminopyrazole residue (this can be substituted by chlorine in its phenyl group K,
(can be substituted by sulfo) or 2-
methyl or 2-phenylindole residue (which can be substituted by ethyl in its 1-position) and R and X have the meaning given in claim 5 Monoaiso dye according to claim 5. Formula 7 (wherein KX R,
The monoaiso dye according to claim 6 (d), which is bonded to the phenyl ring at the 0- or p-position relative to the 22 group. ' 8 K is one methyl-1 or 2-phenylindole residue, ? N',N'-diethyl-3-acetylaminoaniline residue, N,N-diethyl or N,N-dibutyl-3-methylaniline residue, 'N-ethyl-dibutyl-phenethyl-3-jchilua and 1] residue group, 1-phenyl-3-methylaminovirazole residue, and X is hydrogen? , chlorine or methyl, and R is hydrogen, chlorine,
Trifluoromethyl, ethylsulfonyl, p-'7benzoyl, sulfamoyl, N-methylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethynolesulfamoyl? 7. A monoazo dye as set forth in claim 7 which is N-methyl-N-cyclohexylsulfamoyl or N-methyl-N-cyclohexylsulfamoyl. ' 9 The method for producing a monoazo dye according to claim 1, characterized in that the diazo component of the formula is diazotized and coupled to the coupling component of the formula H - K (4) ( In addition,
Are K, R, and X in formulas (3) and (4) patent claims? (has the meaning set forth in Scope No. 1). ? 10
Expression [In the expression, ? R is hydrogen, halogen, C I ""6-alkyl, trifluoromethyl, carboxyl, -so? ~C1
-6-alkyl, -802-R''] group (where R1 is a substituted or unsubstituted phenyl- or naphthyl-01-4-alkyl group, R2 and R3 are each independently hydrogen , C1-6-alkyl or C5-7-cycloalkyl, and R4 is unsubstituted: a substituted phenyl group or halogen, CI'-4-alkyl or C1-4
- refers to a phenyl group which can be substituted by 1802 When bonded to the phenyl ring at the ○1 position with respect to one group, 'R and No] Q compound. 1. I. Claim 10, wherein X is bonded to the sulfophenyl ring in the p-position relative to the TS: 02 group, and R and X have the meanings given in claim 10. Compounds described. 12 A patent claim in which R is a -so2 group (<<whereas 0-but is bonded to the phenyl ring at the p-position, and R and X have the meaning described in claim 11) 13 NH2. One group is bonded to the phenyl ring at the 0-ma or p-position relative to the -802 group, and R
The compound according to claim 12, wherein and X have the meanings given in claim 12. 14 R is hydrogen, . chlorine, methyl, trifluoromethyl, carboxyl, or -SO2C1-2, where R5 is hydrogen or C1-3-alkyl, R6 is hydrogen, C'l-6-alkyl which can be substituted by hydroxyl or methoxy , or cyclohexyl, and R7 means phenyl or chlorophenyl), X means hydrogen, methyl, JM element or ethoxy, and Claim 13: If it is likely to bond to the phenyl ring at the ○1 position with respect to one group, it cannot be hydrogen or chlorine or methyl at the p-position with respect to the -802 group. Compounds described in. Formula 15 (wherein R and compounds). 16. In the method for producing the compound according to claim 10, the formula '?・A compound of the formula (wherein Hal means halogen and R has the meaning given in claim 10) is converted into a compound of the formula (wherein, the terminator is defined in claim io reacts with a compound (having the meaning stated). A method characterized in that the reaction product is sulfonated, and the NO2 group is then reduced to an amino group. - 17 X is hydrogen 1 or halogen, and each independently hydrogen, l. c;,6-alkyl or C5-7
- cycloalyl) in the method for producing the compound according to claim 10 of formula (3),
A compound of formula 1 (wherein Hal means halogen),
reacting with a compound of formula 1 (wherein A process characterized in that the N()2 group is then reduced to an amino group.・18 Patents. A method of using the monoazo dye according to any one of claims 1 to 8 or the monoazo dye obtained by the method according to claim 9 for dyeing and printing. 19. A method for dyeing and printing using the monoazo dye according to claim 1. ．． 20. The method according to claim 19 for dyeing a polyamide fiber. 21 Claims 18 to 20. A dyed or printed material, especially a finely divided material, obtained according to the method described in any of the above.